WO2021210749A1 - Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant - Google Patents

Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant Download PDF

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WO2021210749A1
WO2021210749A1 PCT/KR2020/017886 KR2020017886W WO2021210749A1 WO 2021210749 A1 WO2021210749 A1 WO 2021210749A1 KR 2020017886 W KR2020017886 W KR 2020017886W WO 2021210749 A1 WO2021210749 A1 WO 2021210749A1
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carbon atoms
encapsulant film
alpha
composition
ethylene
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PCT/KR2020/017886
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English (en)
Korean (ko)
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전정호
이은정
공진삼
이영우
이진국
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주식회사 엘지화학
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Priority to US17/779,337 priority Critical patent/US11884801B2/en
Priority to EP20931132.3A priority patent/EP4047051A4/fr
Priority to JP2022535672A priority patent/JP7418900B2/ja
Priority claimed from KR1020200170553A external-priority patent/KR102387101B1/ko
Publication of WO2021210749A1 publication Critical patent/WO2021210749A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J3/00—Processes of treating or compounding macromolecular substances
    • C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
    • H01L31/042—PV modules or arrays of single PV cells
    • H01L31/048—Encapsulation of modules
    • H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/02—Cp or analog bridged to a non-Cp X anionic donor
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2420/00—Metallocene catalysts
    • C08F2420/06—Cp analog where at least one of the carbon atoms of the non-coordinating part of the condensed ring is replaced by a heteroatom
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2810/00—Chemical modification of a polymer
    • C08F2810/20—Chemical modification of a polymer leading to a crosslinking, either explicitly or inherently
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/64—Titanium, zirconium, hafnium or compounds thereof
    • C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
    • C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/08—Copolymers of ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/204—Applications use in electrical or conductive gadgets use in solar cells
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2312/00—Crosslinking
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy

Definitions

  • the present invention relates to a composition for an encapsulant film comprising an ethylene/alpha-olefin copolymer having high volume resistance and light transmittance, and an encapsulant film using the same.
  • a solar cell When a solar cell is used outdoors, such as on the roof of a building, it is generally used in the form of a solar cell module.
  • a protective sheet for solar cell module front side protection member
  • solar cell encapsulant / solar cell encapsulant / crystalline solar cell element / solar cell encapsulant / protective sheet for solar cell module (back side) protection member) in the order of
  • it laminates
  • the solar cell encapsulant an ethylene/vinyl acetate copolymer or an ethylene/alpha-olefin copolymer, which is generally excellent in transparency, flexibility, and adhesion, is used.
  • the volume resistance of the encapsulant decreases as the temperature and humidity of the installed place increase, and a potential difference occurs between the solar cell and the frame.
  • a potential difference occurs between the solar cell and the frame.
  • a phenomenon in which leakage current is generated in the presence of such a potential difference and the power generation efficiency is rapidly reduced is referred to as a PID phenomenon.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2010-258439
  • Another object of the present invention is to provide a method for preparing the composition for an encapsulant film and an encapsulant film prepared by using the composition for the encapsulant film.
  • the present invention provides a composition for an encapsulant film comprising an ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d).
  • melt index Melt Index, MI, 190 °C, 2.16kg load condition
  • the present invention provides an encapsulant film comprising the composition for the encapsulant film.
  • composition for an encapsulant film of the present invention uses an ethylene/alpha-olefin copolymer having a high crystallinity distribution and a low free volume, thereby exhibiting excellent volume resistance and light transmittance, and thus various uses in the field of electrical and electronic industries widely available as
  • composition for an encapsulant film of the present invention is It is characterized in that it comprises an ethylene/alpha-olefin copolymer satisfying the following conditions (a) to (d).
  • melt index Melt Index, MI, 190 °C, 2.16kg load condition
  • the present invention relates to a composition for an encapsulant film having high volume resistance and excellent electrical insulation properties.
  • the ethylene/alpha-olefin copolymer contained in the composition for an encapsulant film of the present invention is used as a catalyst by mixing the transition metal compound represented by Chemical Formula 1 and Chemical Formula 2 during preparation, and the transition metal represented by Chemical Formula 1 Due to the structural characteristics of the catalyst, it is difficult to introduce an alpha-olefin-based monomer to the compound, which tends to produce a high-density copolymer, and the transition metal compound represented by Formula 2 can introduce a large amount of alpha-olefin.
  • a low-density polymer (elastomer) can also be prepared, and the two transition metal compounds have different copolymerizability for incorporating an alpha-olefinic monomer when used alone.
  • the ethylene/alpha-olefin copolymer of the present invention prepared by using a mixed composition thereof as a catalyst has both a low-density region in which a large amount of alpha-olefinic monomer is mixed and a high-density region in which a small amount of alpha-olefin-based monomer is incorporated.
  • a copolymer As a copolymer, it has a wide crystallinity distribution and contains a small amount of free volume, and thus has excellent electrical insulation properties due to low charge mobility.
  • the ethylene/alpha-olefin copolymer contained in the composition for an encapsulant film of the present invention is a low-density polymer having a density in the range of 0.85 to 0.89 g/cc, wherein the density means a density measured according to ASTM D-792 can do. More specifically, the density may be 0.850 g/cc or more, 0.860 g/cc or more, or 0.870 g/cc or more, or 0.874 g/cc or more, and 0.890 g/cc or less, or 0.880 g/cc or less, 0.878 g It can be less than or equal to /cc.
  • the density of the ethylene/alpha-olefin copolymer is affected by the type and content of the monomer used during polymerization, the degree of polymerization, and the like, and in the case of the copolymer, it is greatly affected by the content of the comonomer.
  • a low-density ethylene/alpha-olefin copolymer can be prepared, and the content of the comonomer can be introduced into the copolymer may depend on the inherent copolymerizability of the catalyst.
  • the ethylene/alpha-olefin copolymer contained in the composition for an encapsulant film of the present invention is a copolymer prepared by using the compounds represented by Chemical Formulas 1 and 2 as a catalyst, and exhibits a low density as described above, and as a result, excellent processability can represent
  • the ethylene/alpha-olefin copolymer included in the composition for an encapsulant film of the present invention has a narrow molecular weight distribution (MWD) in the range of 1.8 to 2.3. More specifically, the molecular weight distribution may be 1.80 or more, 1.90 or more, 2.30 or less, 2.20 or less, 2.10 or less, 2.05 or less.
  • the molecular weight distribution increases, and as a result, impact strength and mechanical properties decrease, and there is a possibility that a blocking phenomenon may occur.
  • the polymerizability of the monomer is different for each catalyst, the molecular weight of the finally prepared polymer is affected depending on the type of catalyst. There is a problem that the molecular weight distribution is also widened.
  • an appropriate amount of hydrogen is added during the polymerization reaction to narrow the molecular weight distribution, thereby preventing ⁇ -hydride elimination from randomly occurring in the polymer chain. And it is possible to induce a uniform termination reaction by adding hydrogen.
  • the catalyst structure affects the weight average molecular weight and melt index. It is necessary to determine the appropriate type of catalyst and the amount of hydrogen input within a range that can take both the unique characteristics and the effect of reducing the molecular weight distribution according to the hydrogen input.
  • the transition metal compound represented by Formula 1 and the transition metal compound represented by Formula 2 were mixed and used as a catalyst and an optimal amount of hydrogen was added while preparing, It has a narrow molecular weight distribution within the above-mentioned range, preventing deterioration of crosslinking properties, impact strength, mechanical properties, etc., while exhibiting high volume resistance and electrical insulation.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) are polystyrene equivalent molecular weights analyzed by gel permeation chromatography (GPC), and the molecular weight distribution can be calculated from a ratio of Mw/Mn.
  • the ethylene/alpha-olefin copolymer may have a weight average molecular weight (Mw) of 40,000 to 150,000 g/mol. More specifically, the weight average molecular weight may be 45,000 g/mol or more, 50,000 g/mol or more, or 60,000 g/mol or more, and 130,000 g/mol or less, 100,000 g/mol or less, or 90,000 g/mol or less. .
  • the ethylene/alpha-olefin copolymer included in the composition for an encapsulant film of the present invention has a melt index (Melt Index, MI, 190°C, 2.16kg load condition) of 1 to 100 dg/min.
  • the melt index may be 1 dg/min or more, 2 dg/min or more, 3 dg/min or more, or 4 dg/min or more, and 100 dg/min or less, 20 dg/min or less, or 15 dg/min or more. min or less.
  • the production rate may be reduced due to a high load, and if the melt index is more than 100 dg/min, the volume resistance or light transmittance of the ethylene/alpha-olefin copolymer is lowered, or the film Since molding is difficult, there is a problem in that the use of a solar cell encapsulant composition is not suitable.
  • the ethylene / alpha-olefin copolymer has a melt flow index ( MI 10 ) value measured at 190 ° C. and 10 kg load condition with respect to the melt index (MI 2.16 ) measured at 190 ° C. and 2.16 kg load condition ( MFRR, Melt Flow Rate Ratio, MI 10 /MI 2.16 ) may be 8.0 or less, specifically 4.0 or more, 4.2 or more, 4.5 or more, 8.0 or less, 7.0 or less, and 6.8 or less.
  • the melt flow index is an indicator of the degree of long-chain branching of the copolymer, and the ethylene/alpha-olefin copolymer of the present invention satisfies the melt flow index along with the above-described physical properties, so that it is suitable for a solar cell encapsulant composition, etc. can be applied.
  • the ethylene/alpha-olefin copolymer of the present invention when it has a low melt index of 1 to 100 dg/min as described above, it may have a low melt flow index of 8.0 or less as described above. Since the copolymer of the present invention has such a low melt index and melt flow index, the copolymer has a high molecular weight and a low content of long-chain branches, and thus has excellent crosslinking degree.
  • the conventional copolymer has such a low melt index and melt flow index, and at the same time, it is difficult to have a wide crystallinity distribution because the full width at half maximum (FWHM) of the crystallization peak, which will be described later, is 15 or more.
  • a copolymer was prepared by adding an appropriate amount of hydrogen while using the compound represented by Formula 1 and Formula 2 as a catalyst, and the polymerization was terminated due to the addition of hydrogen, so that the end of the copolymer was saturated and long-chain branches were not formed, so melt flow
  • a copolymer with a low index and a wide crystallinity distribution was prepared by using heterogeneous catalysts with different crystallinity characteristics while at the same time.
  • the ethylene/alpha-olefin copolymer included in the composition for encapsulant film of the present invention has a full width at half maximum (FWHM) of the crystallization peak that appears when the crystallization temperature is measured by cross-fractionation chromatography (CFC). This is over 15.
  • the peak width at half maximum is a value derived from a crystallinity distribution graph plotted with dW/dT values according to temperature measured in a bivariate distribution by cross-fractionation chromatography.
  • the cross-fractionation chromatography is a method combining Temperature Rising Elution Fractionation (TREF) and Gel Filtration Chromatography (GPC). It is a kind of method.
  • a high-temperature sample solution in which an ethylene/alpha-olefin copolymer is completely dissolved in a solvent is injected into a column filled with an inert carrier, and the temperature of the column is lowered to attach the sample to the surface of the filler, and then, in the column While flowing ortho dichlorobenzene, gradually increase the temperature of the column.
  • the concentration of the copolymer eluted at each temperature is detected, and the component eluted at each temperature is sent to GPC online for each fraction at the same time to obtain a chromatogram, and the molecular weight distribution of each component is calculated therefrom.
  • the higher the crystallinity of the eluted component the higher the elution temperature. Therefore, the crystallinity distribution of the copolymer can be known by finding the relationship between the elution temperature and the elution amount (wt%) of the ethylene/alpha-olefin copolymer.
  • the ethylene/alpha-olefin copolymer has a high FWHM value of 15 or more, which indicates that the crystallinity distribution of the copolymer is high. Insulation is excellent.
  • FWHM is related to the uniformity of crystallinity according to the copolymerizability in which the alpha-olefinic monomer is incorporated, and the molecular weight distribution is related to the uniformity of the chain length according to the growth rate of ethylene, etc.
  • the molecular weight distribution is narrow due to constant chain growth, but in the same principle, the copolymerizability is constant and the crystallinity distribution is narrow and the FWHM value is small. It is difficult to prepare the resulting copolymers.
  • an ethylene/alpha-olefin copolymer having a high FWHM value of 15 or more and a narrow molecular weight distribution of 1.8 to 2.3 by using a mixture of heterogeneous catalysts having similar ethylene growth rates and different copolymerizability. has been manufactured
  • the FWHM value may be 15 or more, 16 or more, 16.5 or more, 16.8 or more, 50 or less, 40 or less, 30 or less, 25 or less, or 21 or less.
  • the ethylene/alpha-olefin copolymer included in the composition for an encapsulant film of the present invention may have a melting temperature (Melting Temperature, Tm) of 70° C. or less. More specifically, the melting temperature may be 50 °C or higher, 55 °C or higher, or 58 °C or higher, and 70 °C or lower, 68 °C or lower, 67 °C or lower. By having a melting temperature in such a temperature range, excellent thermal stability may be exhibited.
  • Tm Melting Temperature
  • the ethylene / alpha-olefin copolymer may have a crystallization temperature (Crystallization Temperatur, Tc) of 70 °C or less, 60 °C or less, 55 °C or less, 51 °C or less, 30 °C or more, 35 °C or more, 40 °C or more, 42°C or higher.
  • Tc Crystallization Temperatur
  • the melting temperature and the crystallization temperature may be measured using a Differential Scanning Calorimeter (DSC). Specifically, the copolymer is heated to 150° C. and maintained for 5 minutes, then lowered to 20° C., and then the temperature is increased again. At this time, the rate of rise and fall of the temperature is controlled at 10°C/min, respectively, and the result measured in the section where the second temperature rises is the melting temperature, and the result measured in the section where the temperature is decreased is the crystallization temperature. can do.
  • DSC Differential Scanning Calorimeter
  • the ethylene/alpha-olefin copolymer included in the composition for an encapsulant film of the present invention is prepared by copolymerizing ethylene and an alpha-olefin-based monomer, and in this case, it refers to a portion derived from the alpha-olefin-based monomer in the copolymer.
  • the alpha-olefin is a C4 to C20 alpha-olefin, specifically propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene, 1 -undecene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-eicocene, etc. may be mentioned, and among these, 1 type alone or a mixture of 2 or more types may be mentioned.
  • the alpha-olefin may be 1-butene, 1-hexene, or 1-octene, and preferably 1-butene, 1-hexene, or a combination thereof.
  • the content of the alpha-olefin in the ethylene/alpha-olefin copolymer may be appropriately selected within the range satisfying the above-mentioned physical property requirements, and specifically, more than 0 to 99 mol% or less, or 10 to 50 mol% may be, but is not limited thereto.
  • a modified resin composition for example, a silane-modified resin composition or an amino silane-modified resin composition can be prepared by using the composition for an encapsulant film of the present invention.
  • the composition for the encapsulant film may include a known crosslinking agent, a crosslinking aid, a silane coupling agent, etc. in addition to the above-described ethylene/alpha-olefin copolymer.
  • the crosslinking agent is a radical initiator in the manufacturing step of the silane-modified resin composition, and may serve to initiate a reaction in which the unsaturated silane compound is grafted to the resin composition.
  • the heat resistance durability of the final product can be improved. have.
  • crosslinking agent is a crosslinking compound capable of initiating radical polymerization of a vinyl group or forming a crosslinking bond
  • various crosslinking agents known in the art can be variously used, for example, organic peroxides, hydroperoxides and azo compounds. One or two or more selected from the group consisting of may be used.
  • t-bufilcumyl peroxide di-t-butyl peroxide, di-cumyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, 2,5-dimethyl dialkyl peroxides such as -2,5-di(t-butylperoxy)-3-hexyne; hydroperoxides such as cumene hydroperoxide, diisopropyl benzene hydroperoxide, 2,5-dimethyl-2,5-di(hydroperoxy)hexane and t-butyl hydroperoxide; diacyl peroxides such as bis-3,5,5-trimethylhexanoyl peroxide, octanoyl peroxide, benzoyl peroxide, o-methylbenzoyl peroxide, and 2,4-dichlorobenzoyl peroxide; t-Butylperoxy isobutylate, t
  • the organic peroxide may be an organic peroxide having a 1-hour half-life temperature of 120 to 135 °C, for example, 120 to 130 °C, 120 to 125 °C, preferably 121 °C.
  • the "one-hour half-life temperature” means a temperature at which the half-life of the cross-linking agent becomes one hour. According to the one-hour half-life temperature, the temperature at which the radical initiation reaction efficiently occurs is different, and therefore, when an organic peroxide having a one-hour half-life temperature in the above-described range is used as a crosslinking agent, the lamination process temperature for manufacturing an optoelectronic device In the radical initiation reaction, that is, the crosslinking reaction can proceed effectively.
  • the crosslinking agent is included in an amount of 0.01 to 1 parts by weight, for example, 0.05 to 0.55, 0.1 to 0.5, or 0.15 to 0.45 parts by weight, based on 100 parts by weight of the composition for the encapsulant film, and the crosslinking agent is used in an amount of less than 0.01 parts by weight.
  • the effect of improving the heat resistance properties is insignificant, and when included in excess of 1 part by weight, the moldability of the encapsulant sheet is reduced, and a problem of process restrictions may occur, and the physical properties of the encapsulant may be affected. .
  • the resin composition may include a crosslinking aid in addition to the crosslinking agent.
  • a crosslinking aid included in the resin composition, the degree of crosslinking between the resin compositions by the crosslinking agent can be increased, and thus the heat resistance durability of the final product, for example, an encapsulant sheet can be further improved.
  • crosslinking aid various crosslinking aids known in the art may be used.
  • a compound containing at least one unsaturated group such as an allyl group or a (meth)acryloxy group may be used as the crosslinking aid.
  • the compound containing the allyl group may be, for example, a polyallyl compound such as triallyl isocyanurate (TAIC), triallyl cyanurate, diallyl phthalate, diallyl fumarate or diallyl maleate.
  • the compound containing the (meth)acryloxy group may be, for example, a poly(meth)acryloxy compound such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, or trimethylolpropane trimethacrylate. However, it is not particularly limited thereto.
  • the crosslinking aid is included in an amount of 0.01 to 0.5 parts by weight, for example, 0.01 to 0.3, 0.015 to 0.2, or 0.016 to 0.16 parts by weight, based on 100 parts by weight of the composition for the encapsulant film, and the crosslinking aid is 0.01 parts by weight
  • the effect of improving the heat resistance properties is insignificant, and when included in excess of 0.5 parts by weight, a problem affecting the physical properties of the final product, such as an encapsulant sheet, may occur and the production cost may increase.
  • composition for the encapsulant film may further include a silane coupling agent in addition to the ethylene/alpha-olefin copolymer, a crosslinking agent, and a crosslinking aid.
  • silane coupling agent examples include N-( ⁇ -aminoethyl)- ⁇ -aminopropyltrimethoxysilane, N-( ⁇ -aminoethyl)- ⁇ -aminopropylmethyldimethoxysilane, ⁇ -amino At least one selected from the group consisting of propyltriethoxysilane, ⁇ -glycidoxypropyltrimethoxysilane, and ⁇ -methacryloxypropyltrimethoxysilane (MEMO) may be used.
  • the silane coupling agent may be included in an amount of 0.1 to 0.4 parts by weight based on 100 parts by weight of the composition for an encapsulant film.
  • the adhesion to glass is poor when manufacturing a solar module, so moisture can easily penetrate, so long-term performance of the module cannot be guaranteed.
  • composition for the encapsulant film may further include an unsaturated silane compound and an amino silane compound.
  • the unsaturated silane compound is grafted onto the main chain including the polymerization unit of the monomer of the copolymer of the present invention in the presence of a radical initiator and the like, and may be included in a polymerized form in the silane-modified resin composition or the amino silane-modified resin composition.
  • the unsaturated silane compound is vinyltrimethoxysilane, vinyltriethoxysilane, vinyltripropoxysilane, vinyltriisopropoxysilane, vinyltributoxysilane, vinyltripentoxysilane, vinyltriphenoxysilane, or vinyl It may be triacetoxy silane and the like, and as an example, vinyl trimethoxy silane or vinyl triethoxy silane may be used, but the present invention is not limited thereto.
  • the amino silane compound is an unsaturated silane compound grafted to the main chain of the copolymer in the grafting modification step of the ethylene/alpha-olefin copolymer, for example, a reactive functional group such as an alkoxy group of vinyltriethoxysilane.
  • a reactive functional group such as an alkoxy group of vinyltriethoxysilane.
  • the amino silane compound is not particularly limited as long as it is a silane compound including an amine group, and is a primary amine or a secondary amine.
  • aminotrialkoxysilane, aminodialkoxysilane, etc. may be used as the amino silane compound. Examples include 3-aminopropyltrimethoxysilane (APTMS), 3-aminopropyltriethoxysilane.
  • the content of the unsaturated silane compound and/or the amino silane compound is not particularly limited.
  • composition for the encapsulant film may further include at least one additive selected from a light stabilizer, a UV absorber, and a heat stabilizer, if necessary.
  • the light stabilizer may serve to prevent photooxidation by catching active species that initiate photodegradation of the resin depending on the application to which the composition is applied.
  • the type of the light stabilizer that can be used is not particularly limited, and, for example, a known compound such as a hindered amine-based compound or a hindered piperidine-based compound may be used.
  • the UV absorber absorbs ultraviolet rays from sunlight or the like depending on the use of the composition, converts it into harmless thermal energy in the molecule, and prevents the active species of photodegradation initiation in the resin composition from being excited.
  • Specific types of UV absorbers that can be used are not particularly limited, and for example, inorganic UV such as benzophenone-based, benzotriazole-based, acrylnitrile-based, metal complex salt-based, hindered amine-based, ultra-fine titanium oxide or ultra-fine zinc oxide.
  • One type or a mixture of two or more types, such as an absorbent, can be used.
  • examples of the heat stabilizer include tris(2,4-di-tert-butylphenyl)phosphite, bis[2,4-bis(1,1-dimethylethyl)-6-methylphenyl]ethyl ester phosphorous acid, tetrakis (2,4-di-tert-butylphenyl)[1,1-biphenyl]-4,4'-diylbisphosphonate and bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite phosphorus-based thermal stabilizers; and a lactone-based thermal stabilizer such as a reaction product of 8-hydroxy-5,7-di-tert-butyl-furan-2-one and o-xylene, and one or two or more of the above may be used. have.
  • the content of the light stabilizer, the UV absorber and/or the heat stabilizer is not particularly limited. That is, the content of the additive may be appropriately selected in consideration of the use of the resin composition, the shape or density of the additive, etc., and is usually within the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total solid content of the composition for an encapsulant film. can be appropriately adjusted.
  • composition for an encapsulant film of the present invention may further include various additives known in the art according to the use to which the resin component is applied in addition to the above components.
  • composition for the encapsulant film can be used as various molded articles by molding by methods such as injection and extrusion, and specifically, as an encapsulant for encapsulating elements in various optoelectronic devices, such as solar cells, etc. It may be used, for example, it may be used as an industrial material applied to a temperature rise lamination process, etc., but the use is not limited thereto.
  • the method for producing the composition for an encapsulant film of the present invention comprises polymerizing ethylene and an alpha-olefinic monomer in the presence of a catalyst composition comprising a transition metal compound represented by the following Chemical Formulas 1 and 2, to obtain an ethylene/alpha-olefin copolymer. preparing a coalescence; and mixing the ethylene/alpha-olefin copolymer with a crosslinking agent, a crosslinking aid, and a silane coupling agent.
  • R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms,
  • R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
  • R 4 and R 5 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
  • R 6 to R 9 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
  • Two or more adjacent to each other among R 6 to R 9 may be connected to each other to form a ring
  • Q 1 is Si, C, N, P or S,
  • M 1 is Ti, Hf or Zr
  • X 1 and X 2 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms,
  • R 10 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms,
  • R 11a to R 11e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms,
  • R 12 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms,
  • R 13 and R 14 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
  • R 15 to R 18 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms,
  • Two or more adjacent to each other among R 15 to R 18 may be connected to each other to form a ring
  • Q 2 is Si, C, N, P or S
  • M 2 is Ti, Hf or Zr
  • X 3 and X 4 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms.
  • R 1 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, more specifically, R 1 is methyl, ethyl, propyl, butyl, isobutyl, tibutyl, isopropyl, cyclohexyl, benzyl, phenyl, methoxyphenyl, ethoxyphenyl, fluorine phenyl, bromophenyl, chlorophenyl, dimethylphenyl or diethylphenyl.
  • R 2 and R 3 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms, and more specifically, R 2 and R 3 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
  • R 4 and R 5 are the same as or different from each other, and each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, alkyl having 1 to 6 carbon atoms. More specifically, R 4 and R 5 may be methyl, ethyl or propyl.
  • R 6 To R 9 are the same as or different from each other, and each independently, hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms. More specifically, R 6 to R 9 may be the same as or different from each other, and each independently, may be hydrogen or methyl.
  • At least two of R 6 to R 9 may be connected to each other to form an aliphatic ring having 5 to 20 carbon atoms or an aromatic ring having 6 to 20 carbon atoms, wherein the aliphatic ring or aromatic ring is halogen, carbon number 1 to It may be substituted with alkyl having 20 carbon atoms, alkenyl having 2 to 20 carbon atoms, or aryl having 6 to 20 carbon atoms.
  • Q 1 may be Si, C, N, P or S, and more specifically, Q 1 may be Si.
  • M 1 may be Ti, Hf, or Zr.
  • X 1 and X 2 are the same as or different from each other, and each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; Or it may be an arylamino having 6 to 20 carbon atoms.
  • the compound represented by Formula 1 may be a compound represented by any one of the following Formulas.
  • R 10 is hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; or arylalkyl having 7 to 20 carbon atoms, and more specifically, R 10 is hydrogen; alkyl having 1 to 20 carbon atoms or 1 to 12 carbon atoms; alkoxy having 1 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; arylalkoxy having 7 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; Or it may be an arylalkyl having 7 to 20 carbon atoms.
  • R 11a to R 11e are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryl having 6 to 20 carbon atoms, and more specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; alkoxy having 1 to 12 carbon atoms; or phenyl.
  • R 12 is hydrogen; halogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamido having 1 to 20 carbon atoms; or arylamido having 6 to 20 carbon atoms, and more specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; alkenyl having 2 to 12 carbon atoms; or phenyl.
  • R 13 and R 14 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms.
  • R 15 to R 18 are each independently hydrogen; alkyl having 1 to 20 carbon atoms; cycloalkyl having 3 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; or alkenyl having 2 to 20 carbon atoms, and more specifically, hydrogen; alkyl having 1 to 12 carbon atoms; or cycloalkyl having 3 to 12 carbon atoms, or hydrogen; or methyl.
  • two or more of R 15 to R 18 that are adjacent to each other may be connected to each other to form a ring.
  • Q 2 may be Si, C, N, P or S, and more specifically, Q may be Si.
  • X 3 and X 4 are each independently hydrogen; halogen; alkyl having 1 to 20 carbon atoms; alkenyl having 2 to 20 carbon atoms; aryl having 6 to 20 carbon atoms; alkylaryl having 7 to 20 carbon atoms; arylalkyl having 7 to 20 carbon atoms; alkylamino having 1 to 20 carbon atoms; or arylamino having 6 to 20 carbon atoms, specifically, hydrogen; halogen; alkyl having 1 to 12 carbon atoms; cycloalkyl having 3 to 12 carbon atoms; Or it may be an alkenyl having 2 to 12 carbon atoms, more specifically, hydrogen; Or it may be an alkyl having 1 to 12 carbon atoms.
  • the compound represented by Formula 2 may be any one of compounds represented by Formulas 2-1 to 2-10 below.
  • the molar ratio of the transition metal compound represented by Chemical Formulas 1 and 2 may be 1:0.8 to 1:10, or 1:1 to 1:9, but is not limited thereto.
  • the transition metal compounds represented by Chemical Formulas 1 and 2 used in the present invention have different mixing capabilities of comonomers, and by mixing and using them, a low-density region and a high-density region exist together, resulting in a high crystallinity distribution in the air.
  • a copolymer can be prepared, and the copolymer of the present invention thus prepared exhibits a high crystallinity distribution, a small free volume, and thereby excellent electrical insulation.
  • the polymerization reaction may be carried out by continuously polymerizing ethylene and alpha-olefinic monomers by continuously adding hydrogen in the presence of the catalyst composition, and specifically, while adding hydrogen at 5 to 100 cc/min may be performed.
  • the hydrogen gas serves to suppress the rapid reaction of the transition metal compound in the initial stage of polymerization and terminate the polymerization reaction. Accordingly, an ethylene/alpha-olefin copolymer having a narrow molecular weight distribution can be effectively prepared by controlling the use and amount of hydrogen gas.
  • the hydrogen may be added at a rate of 5 cc/min or more, or 7 cc/min or more, or 10 cc/min or more, or 15 cc/min or more, or 19 cc/min or more, and 100 cc/min or less, Or 50 cc/min or less, or 45 cc/min or less, or 35 cc/min or less, or 29 cc/min or less may be added.
  • the prepared ethylene/alpha-olefin copolymer may implement the physical properties in the present invention.
  • the polymerization reaction does not end uniformly, making it difficult to prepare an ethylene/alpha-olefin copolymer having desired physical properties, In this case, there is a risk that the termination reaction may occur too quickly to produce an ethylene/alpha-olefin copolymer having a very low molecular weight.
  • the polymerization reaction may be carried out at 100 to 200° C., and by controlling the polymerization temperature together with the hydrogen input amount, the crystallinity distribution and molecular weight distribution in the ethylene/alpha-olefin copolymer can be more easily controlled.
  • the polymerization reaction may be carried out at 100 to 200 °C, 120 to 180 °C, 130 to 170 °C, or 130 to 150 °C, but is not limited thereto.
  • a co-catalyst may be additionally used in the catalyst composition to activate the transition metal compound of Formula 1 and/or Formula 2.
  • the cocatalyst is an organometallic compound including a Group 13 metal, and specifically, may include at least one selected from the following Chemical Formulas 3 to 5.
  • each R 19 is independently a halogen radical; a hydrocarbyl radical having 1 to 20 carbon atoms; or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen,
  • a is an integer greater than or equal to 2
  • D is aluminum or boron
  • each R 19 is independently a halogen radical; a hydrocarbyl radical having 1 to 20 carbon atoms; or a hydrocarbyl radical having 1 to 20 carbon atoms substituted with halogen,
  • H is a hydrogen atom
  • Z is a group 13 element
  • A is each independently an aryl having 6 to 20 carbon atoms in which one or more hydrogen atoms may be substituted with a substituent; or alkyl having 1 to 20 carbon atoms,
  • the substituent is halogen; hydrocarbyl having 1 to 20 carbon atoms; alkoxy having 1 to 20 carbon atoms; or aryloxy having 6 to 20 carbon atoms,
  • the [LH] + is trimethylammonium; triethylammonium; tripropylammonium; tributylammonium; diethylammonium; trimethylphosphonium; or triphenylphosphonium,
  • [L] + is N,N-diethylanilinium; or triphenylcarbonium.
  • the compound of Formula 3 may be an alkylaluminoxane-based compound to which repeating units are bonded in a linear, circular or network form, and specific examples include methylaluminoxane (MAO), ethylaluminoxane, isobutylaluminoxane. Or tert- butyl aluminoxane etc. are mentioned.
  • MAO methylaluminoxane
  • ethylaluminoxane ethylaluminoxane
  • isobutylaluminoxane isobutylaluminoxane.
  • tert- butyl aluminoxane etc. are mentioned.
  • the compound of Formula 4 is trimethylaluminum, triethylaluminum, triisobutylaluminum, tripropylaluminum, tributylaluminum, dimethylchloroaluminum, triisopropylaluminum, tri-s-butylaluminum, tricyclopentylaluminum, tri Pentyl aluminum, triisopentyl aluminum, trihexyl aluminum, trioctyl aluminum, ethyl dimethyl aluminum, methyl diethyl aluminum, triphenyl aluminum, tri-p-tolyl aluminum, dimethyl aluminum methoxide, dimethyl aluminum ethoxide, trimethyl boron, and triethylboron, triisobutylboron, tripropylboron, or tributylboron, and in particular, may be trimethylaluminum, triethylaluminum or triisobutylaluminum, but is not limited thereto.
  • the compound of Formula 5 may include a borate-based compound in the form of a trisubstituted ammonium salt, a dialkyl ammonium salt, or a trisubstituted phosphonium salt. More specific examples include trimetalammonium tetraphenylborate, methyldioctadecylammonium tetraphenylborate, triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri(n-butyl)ammonium tetraphenylborate, methyltetradecyclo Octadecylammonium tetraphenylborate, N,N-dimethylaninium tetraphenylborate, N,N-diethylaninium tetraphenylborate, N,N-dimethyl(2,4,6-trimethylanilium)tetraphenylborate, Trimethyl
  • the molecular weight distribution of the finally prepared ethylene/alpha-olefin copolymer may become more uniform, and polymerization activity may be improved.
  • the co-catalyst may be used in an appropriate amount so that the activation of the transition metal compound of Formula 1 and/or Formula 2 can be sufficiently proceeded.
  • the transition metal compound of Formula 1 and/or Formula 2 may be used in a supported form on a carrier.
  • the weight ratio of the transition metal compound and the carrier may be 1:10 to 1:1,000, more specifically, 1:10 to 1:500.
  • the carrier and the transition metal compound are included in a mid-ratio ratio within the above range, an optimal shape may be exhibited.
  • the weight ratio of the promoter to the carrier may be 1:1 to 1:100, more specifically 1:1 to 1:50.
  • the carrier silica, alumina, magnesia, or a mixture thereof may be used, or by drying these materials at a high temperature to remove moisture from the surface, a hydroxyl group or siloxane group having high reactivity on the surface is included. may be used.
  • the high-temperature dried carriers may further include an oxide, carbonate, sulfate, or nitrate component such as Na 2 O, K 2 CO 3 , BaSO 4 and Mg(NO 3 ) 2 .
  • the drying temperature of the carrier is preferably 200 to 800°C, more preferably 300 to 600°C, and most preferably 300 to 400°C. If the drying temperature of the carrier is less than 200 °C, there is too much moisture and the surface moisture and the cocatalyst react. It is undesirable because only the siloxane remains and the reaction site with the co-catalyst decreases.
  • the amount of hydroxyl groups on the surface of the carrier is preferably 0.1 to 10 mmol/g, more preferably 0.5 to 5 mmol/g.
  • the amount of hydroxyl groups on the surface of the carrier can be controlled by the method and conditions or drying conditions of the carrier, such as temperature, time, vacuum or spray drying, and the like.
  • an organoaluminum compound for removing moisture in the reactor is further added, and the polymerization reaction may proceed in the presence of the organic aluminum compound.
  • the organoaluminum compound include trialkylaluminum, dialkyl aluminum halide, alkyl aluminum dihalide, aluminum dialkyl hydride or alkyl aluminum sesqui halide, and more specific examples thereof include Al (C 2 H 5 ) 3 , Al(C 2 H 5 ) 2 H, Al(C 3 H 7 ) 3 , Al(C 3 H 7 ) 2 H, Al(iC 4 H 9 ) 2 H, Al(C 8 H 17 ) ) 3 , Al(C 12 H 25 ) 3 , Al(C 2 H 5 )(C 12 H 25 ) 2 , Al(iC 4 H 9 )(C 12 H 25 ) 2 , Al(iC 4 H 9 ) 2 H, Al (iC 4 H 9 ) 3, (C 2 H 5) , and the like
  • the polymerization pressure may be from about 1 to about 100 Kgf/cm 2 , preferably from about 1 to about 50 Kgf/cm 2 , more preferably from about 5 to about 30 Kgf/cm 2 .
  • the transition metal compound when used in a supported form on a carrier, is an aliphatic hydrocarbon solvent having 5 to 12 carbon atoms, for example, pentane, hexane, heptane, nonane, decane, and isomers thereof and toluene, benzene. It may be dissolved in an aromatic hydrocarbon solvent such as, dichloromethane, or a hydrocarbon solvent substituted with a chlorine atom such as chlorobenzene, or added after dilution.
  • the solvent used here is preferably used by treating a small amount of alkyl aluminum to remove a small amount of water or air that acts as a catalyst poison, and it is also possible to further use a cocatalyst.
  • composition for an encapsulant film of the present invention may be included in the encapsulant film.
  • the encapsulant film of the present invention may be manufactured by molding the composition for encapsulant film into a film or sheet shape.
  • a molding method is not particularly limited, and for example, it may be manufactured by forming a sheet or filming it by a conventional process such as a T-die process or extrusion.
  • the production of the encapsulant film is performed in an in situ process using an apparatus in which the production of the modified resin composition using the composition for the encapsulant film and the film forming or sheet forming process are connected to each other. can do.
  • the thickness of the encapsulant film may be adjusted to about 10 to 2,000 ⁇ m, or about 100 to 1,250 ⁇ m, or about 100 to 1,250 ⁇ m, in consideration of the support efficiency and the possibility of breakage of the device in the optoelectronic device, and the weight reduction or workability of the device. can be changed.
  • the present invention provides a solar cell module including the encapsulant film.
  • the solar cell module fills the gap between the solar cells arranged in series or in parallel with the encapsulant film of the present invention, a glass surface is disposed on the surface where sunlight strikes, and the rear surface is protected with a back sheet.
  • the present invention is not limited thereto, and various types and shapes of solar cell modules manufactured including an encapsulant film in the art may be applied to the present invention.
  • the glass surface may use tempered glass to protect the solar cell from external impact and prevent breakage, and low iron tempered glass with a low iron content to prevent reflection of sunlight and increase the transmittance of sunlight. can be used, but is not limited thereto.
  • the back sheet is a weather-resistant film that protects the back surface of the solar cell module from the outside, and for example, a fluorine-based resin sheet, a metal plate or metal foil such as aluminum, a cyclic olefin-based resin sheet, a polycarbonate-based resin sheet, a poly(meth)acrylic resin a sheet, a polyamide-based resin sheet, a polyester-based resin sheet, a composite sheet obtained by laminating a weather resistant film and a barrier film, and the like, but is not limited thereto.
  • the solar cell module of the present invention may be manufactured without limitation according to a method known in the art, except for including the encapsulant film described above.
  • the solar cell module of the present invention is manufactured using an encapsulant film having excellent volume resistance, and it is possible to prevent electrons in the solar cell module from moving through the encapsulant film to prevent leakage of current to the outside, and thus the insulation deteriorates This can greatly suppress the PID (Potential Induced Degradation) phenomenon in which leakage current occurs and the output of the module decreases rapidly.
  • PID Pressure Induced Degradation
  • the ligand compound (1.06g, 3.22mmol/1.0eq) and MTBE 16.0mL (0.2M) were put in a 50ml Schlenk flask and stirred first. n-BuLi (2.64ml, 6.60mmol/2.05eq, 2.5M in THF) was added at -40°C and reacted at room temperature overnight. After that, MeMgBr (2.68ml, 8.05 mmol/2.5eq, 3.0M in diethyl ether) was slowly added dropwise at -40°C, and TiCl 4 (2.68ml, 3.22 mmol/1.0eq, 1.0M in toluene) was added in this order. The reaction was carried out at room temperature overnight. Then, the reaction mixture was filtered through Celite using hexane. After solvent drying, a brown solid was obtained in a yield of 1.07 g (82%).
  • the ligand compound (1.74 g, 4.14 mmol/1.0eq) and toluene 20.7 mL (0.2 M) were placed in a 50 mL vial and stirred.
  • n-BuLi (3.48 mL, 8.7 mmol/2.1eq, 2.5 M in hexane) was added at -40°C, and the mixture was stirred at room temperature overnight.
  • MeMgBr (4.14 mL, 12.42 mmol/3.0eq, 3.0 M in diethyl ether) was slowly added dropwise at -40°C, and then TiCl 4 DME (1.1 g 4.14 mmol/1.0eq) was sequentially added thereto and overnight at room temperature. stirred.
  • the stirred Li-complex THF solution was cannulated at -78°C in a Schlenk flask containing 2.46 g (1.2 eq, 11.982 mmol) of dichloro(O-tolylmethyl)silane and 30 mL of THF, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo and extracted with 100 mL of hexane.
  • the ligand compound (4.26 g, 10.501 mmol) was added to 53 mL (0.2 M) of MTBE and stirred.
  • n-BuLi (8.6 mL, 21.52 mmol, 2.05eq, 2.5 M in hexane) was added at -40°C, and the mixture was stirred at room temperature overnight.
  • the stirred Li-complex THF solution was cannulated at -78°C in a Schlenk flask containing 8.1 mL (1.0 eq, 49.925 mmol) of dichloro(methyl)(phenyl)silane and 70 mL of THF, followed by stirring at room temperature overnight. After stirring, the mixture was dried in vacuo, and extracted with 100 mL of hexane.
  • An ethylene/alpha-olefin copolymer was prepared in the same manner as in Preparation Example 1, except that polymerization conditions were changed as shown in Table 1 below.
  • the obtained copolymer was vacuum dried to measure the yield, and the results are shown together in Table 1.
  • MI 10 Condition E, 190° C., 10 kg load
  • MI 2.16 Consdition E, 190° C., 2.16 kg load
  • the melting temperature (Tm) and the crystallization temperature (Tc) can be obtained using a Differential Scanning Calorimeter (DSC 6000) manufactured by PerkinElmer, specifically, the temperature of the copolymer under a nitrogen atmosphere using DSC. The temperature was increased to 200°C and maintained for 5 minutes, then cooled to 30°C, and the DSC curve was observed while increasing the temperature again. At this time, the temperature increase rate and the cooling rate were each 10°C/min.
  • DSC 6000 Differential Scanning Calorimeter
  • the melting temperature was determined as the maximum point of the endothermic peak during the second temperature increase, and the crystallization temperature was determined as the maximum point of the exothermic peak during cooling.
  • the weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured for the resulting copolymer under the following gel permeation chromatography (GPC) analysis conditions, and the molecular weight distribution was calculated from the ratio of Mw/Mn.
  • the measuring equipment used was PolymerChar's CFC.
  • a solution of the copolymer using o-dichlorobenzene as a solvent was completely dissolved in an oven in a CFC analyzer at 130° C. for 60 minutes, poured into a TREF column adjusted to 135° C., cooled to 95° C., and stabilized there for 45 minutes. Then, the temperature of the TREF column was lowered to -20°C at a rate of 0.5°C/min, and then maintained at -20°C for 10 minutes. Then, the amount of elution (mass %) was measured using an infrared spectrophotometer.
  • the operation of ramping the temperature rise of the TREF column at a rate of 20 °C/min to a preset temperature and maintaining that temperature at the temperature reached for a preset time (i.e., about 27 minutes) was performed when the temperature of the TREF was 130 °C. Repeat until this, and the amount (mass %) of the fraction eluted during each temperature range was measured.
  • the fraction eluted at each temperature was sent to the GPC column to measure the molecular weight (Mw) in the same manner as in the GPC measurement principle, except that o-dichlorobenzene was used as a solvent.
  • the FWHM value was calculated after fitting the dissolution amount graph (dW/dT vs T) according to the temperature obtained through CFC in the form of a Gaussian curve on the program (Origin).
  • Preparation Examples 1 to 4 which are ethylene/alpha-olefin copolymers according to the present invention, have a high FWHM value of 15 or more, a narrow molecular weight distribution, and also have a density and melt index defined in the present invention. It was confirmed that the range was satisfied.
  • the ethylene/alpha-olefin copolymers of Comparative Preparation Examples 1 and 3 to 5 showed a small FWHM value of less than 15, which resulted in a narrow crystallinity distribution of the copolymer and free volume. It can be seen that the ratio of
  • Comparative Preparation Example 2 had a high melt index
  • Comparative Preparation Example 6 had a high molecular weight distribution
  • Comparative Preparation Example 7 had a high density, confirming that all of them were outside the range defined in the present invention.
  • t-butyl 1-(2-ethylhexyl) monoperoxycarbonate (TBEC) 1 phr (parts per hundred rubber), triallyl isocyanurate (TAIC) 0.5 phr, methacryl 0.2 phr of oxypropyltrimethoxysilane (MEMO) was added to prepare a composition for an encapsulant film. After soaking at 40° C. for 1 hour, it was aged for 15 hours.
  • an encapsulant film having an average thickness of 450 ⁇ m was prepared at a low temperature (extruder barrel temperature of 90° C. or less) to the extent that high-temperature cross-linking would not occur.
  • An encapsulant film was prepared in the same manner as in Example 1, except that the copolymers of Preparation Examples 2 to 4 and Comparative Preparation Examples 1 to 7 were used as samples, respectively.
  • the encapsulant film (15 cm ⁇ 15 cm) with a thickness of 500 ⁇ m prepared above between the two moving films (thickness: about 100 ⁇ m), and in a vacuum laminator, process temperature 150° C., process time 19 minutes 30 seconds (5 minutes vacuum/ 1 min of pressure/13 min of 30 sec of pressure) were laminated to crosslink.
  • volume resistance and total light transmittance (Tt) were measured according to the following method, and are described in Table 3 below.
  • the light transmittance at 550 nm was measured using a Shimadzu UV-3600 spectrophotometer.
  • Example 1 8.8 ⁇ 10 15 91.8
  • Example 2 9.4 ⁇ 10 15 91.7
  • Example 3 9.3 ⁇ 10 15 91.8
  • Example 4 9.0 ⁇ 10 15 90.8 Comparative Example 1 3.0 ⁇ 10 15 90.0
  • Comparative Example 2 3.2 ⁇ 10 15 88.5 Comparative Example 3 3.2 ⁇ 10 15 91.0 Comparative Example 4 5.3 ⁇ 10 15 91.4 Comparative Example 5 4.1 ⁇ 10 15 91.0 Comparative Example 6 6.2 ⁇ 10 15 86.0 Comparative Example 7 6.7 ⁇ 10 15 84.3
  • an encapsulant film is prepared using an ethylene/alpha-olefin copolymer that satisfies all of the density, molecular weight distribution, melt index, and FWHM values defined in the present invention, an excellent level of volume without using a separate additive Resistance and light transmittance could be realized.
  • a solar cell module was prepared using the encapsulant film (thickness 500 ⁇ m) of Example 2 or Comparative Example 3, a fluorine-based back sheet, low iron tempered glass, and a crystalline silicon solar cell.
  • a solar cell module was manufactured while depressurizing the inside of the arrayed module at 150° C. for 20 minutes using a vacuum laminator.
  • the initial output was measured for the solar cell module prepared above, and the loss ratio (%) compared to the initial output was calculated after 288 hours had elapsed under 85°C, 85% RH, and -1,000V.
  • the encapsulant film according to the present invention has excellent volume resistance, it was found that when a solar cell module was manufactured using it, the output decrease due to the PID phenomenon was largely prevented.

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Abstract

La présente invention concerne une composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine ayant une résistivité volumique élevée et une transmittance élevée de la lumière et un film d'encapsulation utilisant la composition.
PCT/KR2020/017886 2020-04-16 2020-12-08 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant WO2021210749A1 (fr)

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US17/779,337 US11884801B2 (en) 2020-04-16 2020-12-08 Composition for encapsulant film comprising ethylene/alpha-olefin copolymer and encapsulant film comprising the same
EP20931132.3A EP4047051A4 (fr) 2020-04-16 2020-12-08 Composition de film d'encapsulation comprenant un copolymère d'éthylène/alpha-oléfine et film d'encapsulation la comprenant
JP2022535672A JP7418900B2 (ja) 2020-04-16 2020-12-08 エチレン／α－オレフィン共重合体を含む封止材フィルム用組成物およびそれを含む封止材フィルム

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KR1020200170553A KR102387101B1 (ko) 2020-04-16 2020-12-08 에틸렌/알파-올레핀 공중합체를 포함하는 봉지재 필름용 조성물 및 이를 포함하는 봉지재 필름
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